New organic phosphorus compounds



United States Patent ()filice 3,016,326 NEW ORGANIC PHGSPHORUS COMPOUNDS Ernst Beriger, Allschwil, Switzerland, assi'gnor to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed Dec. 6, 1960, Ser. No. 73,962 Claims priority, application Switzerland Dec. 9, 1959 24 Claims. (Cl. 167-22-) This invention provides organic phosphorus compounds of the general formula and Z represents an oxygen or sulfur atom, and n and m each represent the whole number 1 or 2.

The Formula 1 includes all the possible stereoisomers, especially the cisand the corresponding trans-isomers. The new compounds are valuable agents for combating pests, especially insect pests and acarids. They are ing 1 to 4 carbon atoms, is condensed with a compound of the formula O=C-R| Hal R in which R ,.R R and R have the meanings given 7 above and Hal represents a halogen atom, such as active against the various stages of development, such I as eggs, larvae and imagines, and they act as contact and stomach poisons.

Especially valuable as insecticides are compounds of the general formula in which R and R each represent an alkyl radical containing 1 to 4 carbon atoms, and advantageously a.

radicals, R represents a hydrogen atom or a chlorine atom, and R represents a lower alkyl radical, more especially a methyl radical or a substituted or unsubsti 'tuted phenyl radical.

The invention also provides a process for the manufacture of the compounds of the above Formula 1, wherein a compound of the formula -methyl or ethyl radical, R and R5 represent lower alkyl' bromine or preferably chlorine, the condensation being accompanied by the splitting off of a compound of the formula R Hal.

The products of the invention can also be obtained by reacting a compound of the formula (5) (Xn-l- /P Me I Y l )m:-l in which R, R 11, m, X, Y and Z have the meanings given above and Me represents; an alkali metal, suchha s sodium, with a compound of the Formula 4. For making compounds in which, R represents a hydrogen atom or an alkyl, radical, the following condensation may be carried out:

The compounds of the above-Formulailused as starting materials are derivatives of trivalent phosphorus, whereas the products of the process of the invention are derivatives of pentavalent phosphorus. Among the compounds of the Formula 3 those in which X, Y and Z each represent an oxygen atom are the most easy to obtain. They correspond, to the formula P-O-Ra a itro and can be made by methods in themselves known.

The aliphatic radicals, which R and R may represent may have straight or branched chains and may be saturated or unsaturated, and they may be substituted or unsubstituted. There may be mentioned, for example, the

7 following groups: methyl, ethyl, propyl, isopropyl, butyl,

Patent ed Jan. 9, 1962 3 carbon atoms. For example, there may be mentioned the following compounds: trimethyl phosphite, triethyl phosphite, tripropyl phosphite, diethyl dodecyl phosphite, tri-(2-cl1lorethyl)-phosphite and the ester of the formula 1P-O CzHa Hz-O CaHsO Among the araliphatic radicals which R and R may represent, there may be mentioned the benzyl radical, and among the cycloaliphatic radicals the cyclohexyl radical and among the heterocyclic radicals the tetrahydrofurfuryl. Starting materials containing such radicals R, for example, cyclohexyl diethyl phosphite, tetrahydrofurfuryl dimethyl phosphite and dibenzyl propyl phosphite. Among compounds in which X and Y each represent a sulfur atom there may be mentioned triethyl thiophosphite of the formula CzHsS PSCzH5 and among those in which X and Y each represent a nitrogen atom, for example, the compounds of the formula flHrDzN P-OCZH5 (czHslfl Compounds of the above Formula 5 are salts of disubstituted phosphites or phosphinic acids, for example, the sodium salt of dimethyl phosphite and diethyl phosphiteof dodecylethyl phosphite, cyclohexylmethyl phosphite, tetrahydrofurfuryl ethyl phosphite or of benzyl ethyl phosphite.

The compounds of the general formula P-Hal R -(Y)m-r are phosphoric acid monohalides, for example, phosphoric acid diethyl ester monochloride, thiophosphoric acid diethyl ester monochloride or bis-dimethylamidophosphoric acid monochloride.

The compounds of the general formula on, are N:O-dialkyl-hydroxylamides of halogenated acyl- .acetic acids, especially acetoacetic, benzoyl acetic, hexahydrobenzoyl acetic, furoyl acetic or tetrahydrofuroyl acetic acid, derived from aliphatic, alicyclic, aromatic or heterocyclic carboxylic acids.

For making the compounds of the invention the reactants are heated at a raised temperature, for example, Within the range of 50 C. to 200 C., and advantageously about 90 C. to 150 C. It may be of advantage to use an inert solvent, such as benzene, toluene, xylene, chloro-benzene or benzine, and if desired, to Work in an atmosphere of an inert gas, for example, under nitrogen and/or under reduced pressure. As stated above, the compounds of the invention are valuable agents for combating pests, especially as insecticides and acaricides.

The invention also provides preparations for combating pests which comprise a compound of the invention as active substance in admixture with a carrier and comprises a method for combating pests with such preparations. Especially advantageous are compounds of the above Formula 2. I

The compounds of the invention can be used for protecting a very wide variety of materials againstpests or harmful insects or aoarids, and gaseous, liquid or solid substances may be used as carriers for the active substance. As such materials to be protected or to be used as carriers there may be mentioned, for example, air, especially inrooms, liquids, for example, water in ponds and finally dead or living solid substrata, for example, objects in living rooms, cellars, attics, stables and also pelts, feathers, wool or the like, and also living organisms of the Vega-- table and animal kingdoms in their very wide variety of stages of development, and provided that they are insensitive to the pest combating agents.

Pests can be combatted with active substances of the invention by the usual methods, for. example, by treating the material to be protected with the active substance in the form of vapor, for example, as a fumigating agent or in the form of a dusting or spraying preparation, for example, solution or suspension prepared with water or a suitable organic solvent, for example, alcohol, petroleum, a tar distillate or the like. There may also be used solutions or aqueous emulsions of organic solvents which contain the active substance and serve for protecting materials or objects by brushing, spraying or dipping.

The spraying or dusting preparations may contain the usual inert fillers or melting agents, for example, kaolin, gypsum or bentonite or other additions, such as sulfite cellulose waste liquor, cellulose derivatives or the like, and also the usual wetting agents or adhesive agents for improving the wetting capacity and adhesive properties of the preparations. The preparations may be made up in powdered form, in the form of aqueous dispersions or pastes, or in the form of self-dispersing oils.

The compounds may be present in the preparations as the sole active substance or in admixture with other insecticides or fungicides. The use of such preparations for plant protection may be carried out by the usual spraying, casting, dusting or fumigating methods.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

EXAMPLE 1 A mixture of 17.25 parts of a-monochloroacetoacetic acid-OzN-dimethyl hydroxylamide and 25 parts by volume of chloro-benzene is heated to 130-140 C. and then (oH3o)2i o 3=C-COr T-O CH:

boiling at l15120 C. under a pressure of 0.02 mm. Hg. Analysis.Calculated: P, 12.23%. Found: P, 12.00%.

The acetoacetic acid-O N-dimethyl hydroxylamide used as intermediate is obtained in simple manner from diketene and O:N dimethyl hydroxylamine. B.P. 84 C.

under 0.5 mm. Hg pressure.

EXAMPLE 2' As described in Example 1, 17.25 parts of tat-1110 10,- chloro-acetoacetic acid-OzN-dimethyl hydroxy-lamide. are reacted in 25 parts by volume of chlorobenzene with 17.55 parts of triethyl phosphite, to yield 25.9 part Of a compound of the formula HZC H (C2H50):] l -0 43:33-00 boiling at 120-126 C. under 0.05 mm. Hg pressure.

' EXAMPLE 3 As described in Example 1, 19.7 parts ofawe-dichloroacetoacetic acid-OzN-dimethyl hydroxylami'de are. re-

acted in 251parts by volume o-fchl'orobenzene with 12.58"

parts of trimethy-l phosphite, to. yield 23 .5 parts. of, acompound of the formula Q HaC Cl Q1333 01130 P-O c=d-o Obi-02GB:

boiling at 130-136" C. under 002 mm. Hg pressure.

Analysis..-Calcula ted: 1?, 10.77%. Found: P,11.1,Q%.

EXAMPLE 4 As described in Example 1., 19.7 parts of mot-dichloracetoacetic acid-OzN-dimethyl hydroxyl amide are reacted in 25 parts by volume of chlorobenzene with 16.8

parts of triethyl phosphite, to yield 26.5 parts of av compound of the formula I (H) H30. (31 (Fm (CgH O)rP-O J=CCONO CH3 boiling at131-135 C. under 0.02 Hgpressure.

EXAMPLE 5' A mixture of 15.3 parts of a-monochloroacetoacetic acid-OzN-diethyl hydroxylamide and 'parts by volume of chlorobenzene is heated to the boil and treated drop.-

vvise with 11 parts of trimethyl phosphite. To, complete the reaction, the mixture is heated for another hour at 130-140 C., by which time 3.1 parts of methyl chloride 2 have been collected; in a cooled receptacle. The volatile constituents are removed in vacuo, to leave as residue 19.2 parts of a compound of the, formula $12 H36" 1'3 CzHg. cE3o)iP-od=c-c01-r oc.n.

boiling at 115 C. under 0.01 mm. Hg pressure.

Analysis.Calculated: P-, 11.02%. Found: P, 11.20%. The acetoacetic acid-OzN-diethyl hydroxylamide used as intermediate is obtained in simple manner from diketene and OzN-diethyl hydroxylamine. B.P. 82-83 C. under 0.2 mm. Hg pressure. a

EXAMPLE 6.

As described inExample 5, 15.3 parts of a-monochlorw acetoacetic acid-Oz'N-diethyl hydroxylamide are reacted in 30 parts by volume of chlorobenzene with 14.7 parts of triethyl phosphite, to yield 21.6 parts of a compound of the formula E30 C135 (C H O-)2P0JJ=C- CON-OC2H5 boiling at 140 C. under 0.01 mm. Hg pressure.

Analysis-Calculated: P, 10.01%. Found: P, 10.00%.

' EXAMPLE 7 As described in Example 5, 182 parts. of u:a-dichloro.--

acetoacetic acid-OzN-diethyl hydroxylamide are reacted in 30 parts by volume of chlorobenzene with 1 1.2 parts. of

6 trimethyl phosphite, toy ie'1d239'5 parts of. a compound of the formula 0 H30 01 I CzHr, QHaQ'),| !-'Q-= l-Q0-1$ T- Q C2111 which decomposes when it is attempted to distil it in a high vacuum.

Analysis.-Calculated: P, 9.81%. Found: P, 7.80%.

EXAMPLE 8 As described in Example 5, 18.2 parts of azu-dichloroacetoacetic acid-O:N-diethy1 hydroxylamide are reacted in 30 parts by volume of chlorobenzene with 14.9 parts of triethyl phosphite, to yield 26.3 parts of a compound of the formula which decomposes when it is attempted to distil it in a high vacuum.

A-nalysis.-Calculated: P, 9.01%. Found: P, 9.30%.

EXAMPLE 9 EXAMPLE 10:

As described in Example 5-, 13.2 parts of a-mono'chloroacetoacetic. acid 0+methy1 N-isopropyl hydroxylamide are reacted in 20 parts by volume ofchlorobenzene with 11.6 parts of triethyl phosphite, to yield 19.3 parts of a compound of the formula (61330 a: clawed) armour-0d=o-ooN-ocm Analysis.-.Calculated: P, 10.01%. FoundrP, 10.00%.

' EXAMPLE 11 As described in Example 5, 15.9 parts of u:a-dichloro acetoacetic acid-O*methyl-N-isopropyl hydroxylamide are reacted in 20 parts by volume of chlorobenzene. with 8.95 parts of trimethyl phosphite, to yield. 19.7 parts of a compound of the formula I v 0113C Cl 03117650) Q (CH'aOh-POC=C-CON-OCHLr a Y Analysisr-Cal'culatedz P, 9.81%.. Found: P, 9.20%.

EXAMPLE 12 As described in Example 5', 15.9 parts of uza-dichloroacetic acid-O-methyl-N-isopropyl hydroxylamide arehreacted in 20 parts by volume of chlorobenzene with 12.0 parts of triethyl phosphite,, to yield. 21.8 parts of a compound of the formula H30 01 C3H7(iS0) V (C H O)qP-OC=O-CONOOH;

Analysist-Calculated: P, 9.01%. Found: P, 9.10%.

Y EXAMPLE 13 As described in Example 5, 17.95 parts of a-monochloroacetoacetic acid-OzN-dimethyl hydroxylamide are reacted in 30 parts by volume of chlorobenzene with I and 0.01% of active principle.

, 7. 22.3-parts oftriisopropyl phosphite, to yield 27.8 parts of a compound of the formula 7 .0 HzC H OH:

. 8 sprayed all over and after 48 hours the effect achieved was examined. When a 100% effect was achieved, the plants were re-infested with fresh aphids and the effect was checked after another period of, 48 hours. The results thus obtained are summarized in the following -Anr1lysisl-- Calculated: P, 100%. Found: P, 9.9%. Table I:

. Table l EFFECT ON APHIDS AFTER 4s nouns Concentr.

of liquid Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. pray, 1 2 3 4 5 6 7 8 9 10 11 12 percent 48 HOURS AFTER RE-INFESTATION 08 -l-+ 0. 04 02 l 0.01 l

When it is attempted to distil it in a high vacuum, the

compound decomposes.

For each plant a symbol was used, namely: signifies that no living aphids were left signifies unsatisfactory or no effect signifies good effect, only a few living aphids left.

:(B) To examine the effect on aphids by diffusion through the leaves the following experiment was conducted with the use of liquid sprays containing, respectively, 0.08%, 0.04%, 0.02% and 0.01% of active principle.

Broad beans, the leaves of which were infested on the underside with aphids, were sprayed only on the upper surface of the leaves with the aforementioned liquid sprays, and after 48 hours the effect on the underside of the leaves was examined. The results thus ob- 2 parts of a condensation product obtained as described 0 tained are summarized in the following Table II.

Table II EFFECT ON APHIDS concentrate and can be emulsified by being poured into water. 7

(A) To examine its contact effect on aphids, the following experiment was carried out with the use of liquid sprays containing respectively, 0.08%, 0.04%, 0.02%

Broad beans, strongly infested with aphids, were Concentr.

of liquid Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12

spray, 7 percent l l l t l l l 0.04 l1 Illl 1. ill i l l I l l l /l --l (C) To examine the so-called systemic action, the

following experiment was conducted with liquid sprays containing, respectively, 0.08%, 0.04%, 0.02% and 0.01% of active principle.

From broad beans (Vivia fabae) which were strongly infested with aphids .(Doralis fabae), the bottom leaves were removed and a color mark was made halfway up the stem. The lower halves of the 'stemsof 2 plants each were sprayed with the liquid spraysof the concentrations mentioned above. After 48 hours the effect of the spraying was checked on the upper, unsprayed halves of the plants. The results thus obtained are summarized in Table III.

Table III EFFECT ON APHIDS AFTER 48 HOURS Goncentr. r V v of liquid Ex. 'Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. spray, 1 2 3 4 6 6 v 7 8 9 10 11 12 percent The compounds obtained in Examples 1 to 6 and 8 4. The compound of the :formula to 12 display a good to very good acaricldal effect on 02H5 0 H 0 the red spinner mite Tetranychus z/z'rticae, and the com- \ll 1 H pounds 1 to 12 are efiicient stomach poisons in the case of Musca domestica, Carausiugmorosus, Orgyia gonoi C2H51O' Hs stigma and Gastroidea viridula. 1 5 The compound of the formula If desired, spray concentrates can also be prepared 1 with wetting agents and emulsifiers other than those Qfi mentioned above. There are suitable non-ionic sub- I I ?O-- 6:.=sQ-*Q"N stances, for example condensation products of aliphatic m 62H) CH3 alcohols, amines or carboxylic acids containing a longchain hydrocarbon, residue of about 10 to 30 carbon 6. The compound of the formula atoms with ethylene oxide, such as the condensation 0' 0 011 H 0 6 115 products of octadecyl alcohol With 25 to 30 mols of \ll v l ethylene oxide, or soybean fatty acid with 30 mols of 5 ethylene oxide, or commercial oleylarnine with mols of ethylene ox de, or dodecylrnereaptan w th 12 mols The compoundrof the f ul f. y n i Am g sui abl amom em ls fier there y be n n d h sodium t: d deeyl co- CHSO E f hol sulfonic acid ester, sodium salt of dodecyl benzene- P00=00N iso' sulfonic acid, potassium or triethanolarnine salt of oleic CHaO or abietic acid or of mixtures of said acids, or the sodium salt of a petroleum sulfonic acid.

Instead of isopropanol there may be used other solvents v for the preparation of liquid spray concentrates, for ex- Patlble earner an orgamc Phosphorus 8. A preparation for combating insectsand acarids which comprises in admixture with an-inertfand comcompound of the ample ethanol, methanol, butanol, acetone, methylethyl general formula ketone, methylcyclohexanol, benzene, toluene, xylene, R0 R kerosenes or petroleum fractions. Mixtures of two or j more solvents can, of course, likewise be used. It I].

- Pip-0 0 0-K, EXAMPLE 16 I t O 2 parts of one of the condensation products according OR to Examples 1 to 6, 9 or 10 are mixed with 9 parts of 4 chalk and 1 part of Wetting agent. A spray powder is obtained from which liquid spray can be prepared by 3 R: suspending it in water. When the walls of stables are l treated with such a liquid spray containing 0.04% of in hi R and 1 h represent an a kyl radicfllcorb active principle, good results are obtained in combating I i i g 1 to 13 ar n. atoms, 2 a d. R3 h represent a flies and midges. lower alkyl radical, R represents a member selectedirom What is claimed is: i 40 the group consisting of a hydrogen atom, a lower alkyl 1. An organic phosphorus compound which is repreradical and a Chlorine atom and srepresents a lower sented by the general formula .alkyl radical.

- R5 9. A preparation for combating insects and ,acarids I which comprises in admixture with an inert and comfi" patible carrier an organic phosphorus compoundof the R1--O 0 0-12, general formula 1 a 0 1 RO CH3 l 0 OR; P-O-C N 111-04? Ra V /O in which R and R each represent an alkyl radical con- 0 0R; taining l to 18 carbon atoms, R and R -each represent a lower alkyl radical, R represents a member selected from the group consisting of a hydrogen atom, a lower alkyl 55 R3 fif i g gi i atom and R5 represents lower in which R, R R and R each represent an alkyl radical y containing 1 to 3 carbon atoms.

2. An organic phosphorus compound which is represented by the general formula 10. A preparat on for combating msects and acarids which comprises in admixture with an inert and com- E 6 patible carrier the compound of the formula P-OO I v '/II II CH0 0 on H 0 on rat-0o 0H \M 1," 3

O P-,0o:=o.-cn OR omo 00m N 11. A preparation for combating insects and acarids which comprises in admixture with an inert and compatin which R, R R and R each represent an alkyl radical lble earner m of thc fQrml-lla containing 1 to 3 carbon atoms. OQHPO 0 CH3 0' CH5 3. The compound of the formula I H HO 0 OH H 0 CH C a \u 1 3 I u. p 3 e,rr, o QOHa CHQO/ 12. A preparation for combating insects and acarids 11 which comprises in admixture with an inert and compatible carrier the compound of the formula CzHiO O t OH; 01 0113 \II I ""II I P O C v 2 v i 0 0011s 13. A preparation forcombating insects and acarids which comprises in admixture with an inert and compatible carrier the compound of the formula CH3() 0 CH3 H 0 02115 A preparation for combating insects and acarids which comprises in admixture with an inert and compatlble carrier the compound of the formula onto 0 on; 11 o C H1 CHaO OCHa 15. The method of controlling insects and acarids on plants, which comprises applying to plants that are subject to attack by said pests in insecticidal and acaricidal amount of an organic phosphorus compound which is represented by the general formula -,in which R, R R and R each represent an alkylradical containing 1 to 3 carbon atoms 17. The method of controlling insects and acarids on plants, which comprises applying toplants that are subject to attack by insects and acarids a pesticidal amount of the compound of the formula CHaO 0 CH3 H II I l OOH:

18. The method of controlling insects and acarids on plants, which comprises applying to plants that are subject to attack by said pests in insecticidal and acaricidal amount of the compound of the formula CH -O\fi (EH3 111 /CH:

-P-O--C'--C-ON 19. The method of I controlling insects and acarids on plants, which comprises applying to plants that are subject to attack by said pests in insecticidal and acaricidal .amount of the compound of the formula 20. The method of controlling insects and acarids on plants, which comprises applying to plants that are subject. to attack by pests in insecticidal and acaricidal amount of the compound of the. formula OH: H O I II 21. The method of controlling insects and acarids on plants, which comprises applying to plants that are subject to attack by said pests in insecticidal and acaricidal amount of the compound of the formula onto 0 cm 11 o l i 'O-( l=( 3 N iso CHaO OCHs 22. An organic phosphorus compound which is represented by the general formula in WhichR, R R and R each represent an alkyl rad ical containing 1 to 3 carbon atoms.

23. A preparation for combating insects and acarids which comprises in admixture with an inert and compatible carrier an organic phosphorus compound of the 1 general formula in which R, R R and R each represent an alkyl radical containing 1 to 3 carbon atoms.

24. The method of controlling insects and acarids on plants, which comprises applying to plants that are subject to attack by said pests an insecticidal and acaricidal amount of-an organic phosphorus compound which is represented by the general formula in which R, R R and R each represent an alkyl radical containing 1 to 3 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Whetstone et al. Aug. 13, 1957 Metivier July 5, 1960 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. January 9, 1962 Ernst Beriger It is "hereby certified that error appears in the abeve numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3 line 30 for "R read R}, are 3 column 5 lines 21 to 25 the formula should appear as shown below instead of as in the patent:

column 11 lines 24 44,, and 69 and eolumn 12 lines 2 10 and 18,, for "in", each occurrenceread an Signed and sealed this 25th day of September 1962a (SEAL) Attest:

ERNESTWISWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

15. THE METHOD OF CONTROLLING INSECTS AND ACARIDS ON PLANTS, WHICH COMPRISES APPLYING TO PLANTS THAT ARE SUBJECT TO ATTACK BY SAID PESTS IN INSECTICIDAL AND ACARICIDAL AMOUNT OF AN ORGANIC PHOSPHORUS COMPOUND WHICH IS REPRESENTED BY THE GENERAL FORMULA 